Oxidation and Hot Corrosion of Gradient Thermal Barrier Coatings Prepared by EB-PVD

The performances of gradient thermal barrier coatings (GTBCs) produced by EB-PVD were evaluated by isothermal oxidation and cyclic hot corrosion (HTHC) tests. Compared with conventional two-layered TBCs, the GTBCs exhibite better resistance to not only oxidation but also hot-corrosion. A dense Al2O3 layer in the GTBCs effectively prohibites inward diffusion of O and S and outward diffusion of Al and Cr during the tests. On the other hand, an "inlaid" interface, resulting from oxidation of the Al along the columnar grains of the bond coat, enhances the adherence of AI2O3 layer. Failure of the GTBC finally occurred by cracking at the interface between the bond coat and AI2O3 layer, due to the combined effect of sulfidation of the bond coat and thermal cvcling.     

Influence of Water Vapor on the Isothermal Oxidation Behavior of Thermal Barrier Coatings

The oxidation of specimens with thermal barrier coating (TBC) consisted of nickel-base superalloy, low-pressure plasma sprayed Ni-28Cr-6AI-0.4Y (wt pct) bond coating and electron beam physical vapor deposited 7.5 wt pct yttria stabilized zirconia (YSZ) top coating was studied at 1050℃ respectively in flows of 02, and mixture of O2 and 5%H2O under atmospheric pressure. The thermal barrier coating has relatively low oxidation rate at 1050℃ in pure O2. Oxidation rate of thermal barrier coating in the atmosphere of O% and 5%H2O is increased The oxidation kinetics obeys almost linear law after long exposure time in the presence of 5% water vapor. Oxide formed along the interface between bond coat and top coat after oxidation at 1050℃ in pure O2 consisted of Al2O3, whereas interfacial scales formed after oxidation at 1050℃ in a mixture of O2 and 5%H2O were mainly composed of Ni(AI,Cr)2O4,NiO and AI2O3. It is suggested that the effect of water vapor on the oxidation of the NiCrAlY coating may be attributed     

Modification of NiCoCrAlY with Pt: Part Ⅰ. Effect of Pt depositing location and cyclic oxidation performance

Pt layers of 5 μm in thickness were electroplated before or after depositing NiCoCrAlY coating by arc ion plating(AIP) aiming for identifying the effect of Pt enriching position on microstructure and cyclic oxidation behavior of Pt modified NiCoCrAlY coatings. Al-rich zones formed at the same position of Ptrich zones for both modified coatings due to uphill diffusion of Al driven by Pt. Cyclic oxidation tests at 1000 and 1100?C indicated that oxidation resistance of NiCoCrAlY was improved by Pt modification via different mechanisms: at surface, Pt-rich zone promoted selective oxidation of Al to form α-Al_2O_3,whilst at coating/substrate interface Pt-rich zone acted as effective diffusion barrier for titanium. Roles of Pt played in enhancing the oxidation performance of various Pt-modified NiCoCrAlY coating were investigated.     

Microstructure Characteristics of Interaction Layer of Zn-Al Eutectic Alloy with Al_2O_3p/6061Al Composites

The interaction between Zn-AI eutectic alloy and Al203p/6061AI composites in the vacuum furnace was investigated. Great attention has been paid to the elements diffusion, the microstructure and formation of the interface between Zn-AI eutectic alloy and Al2O3p/6061AI composites. Experimental results show that Zn-AI eutectic alloy has a good wetting ability to Al2O3p/6061 Al composites and the wetting angle decreases with increasing the temperature in vacuum. After the interaction, an interaction layer forms between Zn-AI alloy and Al2O3p/6061 Al composites. The phases in the interaction layer mainly consist of α-AI(Zn), Al2O3 and CuZn5 resulted from the diffusion of elements from the Zn-AI alloy. Several porosities distribute in the region near the interface of the Zn-AI alloy/interaction layer. The amount of shrinkage voids in the interacting layer is relevant to the penetration of Zn element into Al2O3p/6061Al composites which is a function of temperature. So it is necessary to lower heating temperat     

Modification of NiCoCrAlY with Pt: Part Ⅱ. Application in TBC with pure metastable tetragonal(t’) phase YSZ and thermal cycling behavior

A thermal barrier coating system comprising Pt-modified NiCoCrAlY bond coating and nanostructured 4mol.% yttria stabilized zirconia(4YSZ, hereafter) top coat was fabricated on a second generation Ni-base superalloy. Thermal cycling behavior of NiCoCrAlY-4 YSZ thermal barrier coatings(TBCs) with and without Pt modification was evaluated in ambient air at 1100?C up to 1000 cycles, aiming to investigate the effect of Pt on formation of thermally grown oxide(TGO) and oxidation resistance. Results indicated that a dual layered TGO, which consisted of top(Ni,Co)(Cr,Al)_2O_4 spinel and underlying α-Al_2O_3, was formed at the NiCoCrAlY/4 YSZ interface with thickness of 8.4μm, accompanying with visible cracks at the interface. In contrast, a single-layer and adherent α-Al_2O_3 scale with thickness of 5.6μm was formed at the interface of Pt-modified NiCoCrAlY and 4 YSZ top coating. The modification of Pt on NiCoCrAlY favored the exclusive formation of α-Al_2O_3 and the reduction of TGO growth rate, and thus could effectively improve overall oxidation performance and extend service life of TBCs. Oxidation and degradation mechanisms of the TBCs with/without Pt-modification were discussed.     

Influence of Sputtered NanocrystaUine Coating on Oxidation and Hot Corrosion of a Nickel-based Superalloy M951

The isothermal and cyclic oxidation behaviors in air and hot corrosion behaviors in Na2SO4 ＋ 25 wt% K2SO4 salt of M951 cast superalloy and a sputtered nanocrystalline coating of the same material were studied. Scanning electron microscopy, energy dispersive X-ray spectroscope, X-ray diffraction, and transmission electron microscopy were employed to examine the morphologies and phase composition of the M951 alloy and nanocrystalline coating before and after oxidation and hot corrosion. The as-sputtered nanocrystalline layer has a homogeneous y phase structure of very fine grain size （30-200 nm） with the preferential growth texture of （111） parallel to the interface. Adherent AI203 rich oxide scale formed on the cast M951 alloy and its sputtered coating after isothermal oxidation at 900 and 1000 ℃. However, when being isothermal oxidized at 1100℃ and cyclic oxidized at 1000 ℃, the oxide scale formed on the cast alloy was a mixture of NiO, NiAl2O4, Al2O3 and Nb205 and spalled seriously, while that formed on the sputtered coating mainly consisted of Al2O3 and was very adherent. Nanocrystallization promoted rapid formation of Al2O3 scale during the early stage of oxidation and enhanced the adhesion of the oxide scale, thus improved the oxidation resistance of the substrate alloy. Serious corrosion occurred for the cast alloy. The sputtered nanocrystalline coating apparently improved the hot corrosion resistance of the cast alloy in the mixed sulfate by the formation of a continuous Al2O3 and Cr2O3 mixed oxide layer on the surface of the coating, and the pre- oxidation treatment of the coating led to an even better effect.     

An Aluminide Surface Layer Containing Lower-Al on Ferritic-Martensitic Steel Formed by Lower-Temperature Aluminization

An aluminide(AlFe and α-(FeAl)) surface layer containing lower-Al was formed on ferritic-martensitic steel P92 by means of surface mechanical attrition treatment(SMAT) combined with a duplex aluminization process at lower temperatures,i.e.a packed aluminization followed by a diffusion annealing treatment below its tempering temperature.Indentation tests indicated that the lower-Al surface layer formed on the SMAT sample is more resistant to cracking and has better adhesion to the substrate in comparison with the Al_5Fe_2 layer formed on the as-received sample after the duplex aluminization process.Isothermal steam oxidation measurements showed that the oxidation resistance is increased significantly by the lower-Al surface layer due to the formation of a protective(Fe,Cr)Al_2O_4 layer.The rate constant of oxidation was estimated to decrease from-0.849 mg~2 cm~(-4)h~(-1) of the as-received material to~0.011 mg~2 cm~(-4) h~(-1) of the AlFe layer at 700 ℃.     

Solid-State Interfacial Reaction between Eutectic Au-Ge Solder and Cu/Ni(P)/Au Metalized Ceramic Substrate and Its Suppression

Eutectic Au-12 Ge solder was employed to bond the SiC power devices to a Si_3N_4/Cu/Ni(P)/Au multilayered substrate.The high-temperature reliability of the bond was investigated in detail at 200,250,300 and 330 ℃,respectively.NiGe and Ni_5Ge_3 intermetallic compounds(IMCs) were identified at the Au-12Ge/Ni(P) interface by micro X-ray diffraction(μXRD) and scanning electron microscopy(SEM)equipped with energy dispersive X-ray analysis(EDX).The growth of the Ni-Ge IMCs was dominated by Ni_5Ge_3 layer,which formed at the Ni_5Ge_3/NiGe interface by outward diffusion of Ni from the Ni(P) layer.The activation energy of the total Ni-Ge IMCs growth was 66 kJ/mol.The shear strength of the bond was tested at both 25 ℃ and the aging temperatures,respectively.The shear strength decreased slightly after aging at 200 and 250 ℃.The shear strength tested at 250 ℃ was 46 MPa after aging at 250 ℃ for 3000 h.The shear strength aged at 300 and 330 ℃ rapidly decreased with aging time due to the rapid growth of the Ni_5Ge_3 IMC.To slow down the interfacial reaction between the high temperature solder and the Ni(P)layer,an approximately 200 nm-thick Ta/TaN/Ta new diffusion barrier(DB) was deposited on the substrate.Analysis by transmission electron microscopy(TEM) equipped with EDX,reveals that the Ta/TaN/Ta DB was bonded well to the Ni(P) layer and the solder.High temperature storage test at 330 ℃ for1500 h reveals that the bond of the SiC devices maintained its high shear strength of approximately56 MPa without decrease.The new DB effectively suppressed the interfacial reaction between the Au-12 Ge solder and the Ni(P) layer of the substrate.     

Study of the Interface between Steel Insert and Aluminum Casting in EPC

The effective surface treatment method for steel insert composited with Al base metal by expendable pattern casting （EPC） process and the bonding interface between steel insert and Al base metal were investigated.It was found that Zn plating on steel insert was effective on improving the bonding property between steel insert and Al base metal in EPC process.Zn is thought to promote the formation of diffusion layer.But almost none content of Zn was observed in the boundary which had been plated on the steel insert.A diffusion layer consisting of Al,Si and Fe was formed at the insert/alloy interface and its hardness was higher than the steel insert as matter of course Al base metal.This layer turned out to be intermetallic compounds of Al-Si-Fe system.Higher pouring temperature promoted the diffusion of Fe into Al alloy,so Fe content in intermetallic layers increased at higher pouring temperature.The layer nearest to steel disappeared due to applied pressure.     

Interfacial Structure and Formation Mechanism of Ultrasonic-assisted Brazed Joint of SiC Ceramics with Al—12Si Filler Metals in Air

Ultrasonic-assisted brazing of SiC ceramics was performed by filling with an Al—12Si alloy at a low temperature of 620 °C in air. The interfacial characteristics and formation mechanism were investigated. The joint shear strength reached 84–94 MPa using the ultrasonic time of 2–16 s. The fracture morphology showed that the fracture path initiated and propagated in the joint alloy. The thin film of amorphous SiO 2 that formed on the SiC surface was non-uniformly decomposed and diffused into the liquid Al—12Si alloy under the cavitation erosion effect of ultrasound. Abnormal isolated blocks of Al_2 SiO_5 compounds formed at the interface between Al—12Si and a thicker SiO_2 layer formed during the thermal oxidation treatment of the Si C ceramic. The SiO_2 layer on the Si C ceramic did not hinder or impair the wetting and bonding process, and a stronger bond could form between Al—12Si and SiO_2 or Si C in ultrasonicassisted brazing.     

A study on gradient thermal barrier coatings by EB-PVD in a cyclic high-temperature hot-corrosion environment

Gradient thermal barrier coatings (GTBCs) have been produced by electron beam physical vapor deposition (EB-PVD). Their performance was evaluated by isothermal oxidation and cyclic high-temperature hot-corrosion tests. It is found that the GTBCs exhibited better resistance to high-temperature oxidation and cyclic high-temperature hot-corrosion (HTHC) than traditional two-layered TBCs. A dense Al₂O₃ layer on the bond coat of GTBCs can effectively prohibit inward diffusion of oxidants such as O and S and outward diffusion of Al and Cr. On the other hand, an inlaid interface, the formation of which resulted from the oxidation of Al diffusion into the gaps between the columns of bond coat during the fabrication of the GTBCs, contributes to reinforce the adherence of the Al₂O₃ layer to the bond coat. During fluxing of the Al₂O₃ layer, S and O diffused into the bond coat. Cracks developed in the surface layer of bond coat by the combined effect of sulfidation of the bond coat and thermal cycling, and finally led to failure of the GTBC.     

Einfluss einer PVD‐Al‐Zwischenschicht auf die Eigenschaften eines thermisch gespritzten Wärmedämmschichtsystems nach Temperaturwechselbelastung

Thermal barrier coatings (TBC) generally consist of a metallic bond coat (BC) and a ceramic top coat (TC). Co–Ni–Cr–Al–Y metallic super alloys and Yttria stabilised zirconia (YSZ) have been widely used as bond coat and top coat for thermal barrier coatings systems, respectively. As a result of long‐term exposure of thermal barrier coatings systems to oxygen‐containing atmospheres at high temperatures, a diffusion of oxygen through the porous ceramic layer occurs and consequently an oxidation zone is formed in the interface between ceramic top coat and metallic bond coat. Alloying components of the BC layer create a so‐called thermally grown oxides layer (TGO). One included oxide type is α‐Al₂O₃. α‐Al₂O₃ lowers oxygen diffusion and thus slows down the oxidation process of the bond coat and consequently affects the service life of the coating system positively. The distribution of the alloying elements in the bond coat layer, however, generally causes the formation of mixed oxide phases. The different oxide phases have different growth rates, which cause local stresses, micro‐cracking and, finally, delamination and failure of the ceramic top coat layer. In the present study, a thin Al inter‐layer was deposited by DC‐Magnetron Sputtering on top of the Co–Ni–Cr–Al–Y metallic bond coat, followed by thermal spraying of yttria‐stabilised zirconia (YSZ) as a top coat layer. The deposited Al inter‐layer is meant to transform under operating conditions into a closed layer with high share of α‐Al₂O₃ that slows down the growth rate of the resulting thermally grown oxides layer. Surface morphology and microstructure characteristics as well as thermal cycling behaviour were investigated to study the effect of the intermediate Al layer on the oxidation of the bond coat compared to standard system. The system with Al inter‐layer shows a smaller thermally grown oxides layer thickness compared to standard system after thermal cycling under same conditions.     

TGO对热障涂层失效的作用分析

热生长氧化物(TGO)的形成与长大是热障涂层失效的根本原因。先在IC10高温合金基体上超音速火焰喷涂(HVOF)NiCoCrAlTaY粘结层(BC层),再等离子喷涂二元稀土氧化物稳定氧化锆Sc2O3-Y2O3-ZrO2,喷涂样在1 100℃恒温氧化,利用扫描电镜(SEM)、能谱仪对断面形貌、成分进行分析,讨论了TGO的形成机理及其与热障涂层失效的关系。结果表明:随着恒温氧化时间增加,TGO层底部的Al含量下降,上部、中间弥散颗粒及底部的Ni含量均增加,上部、中间弥散颗粒中Cr含量均减少;喷涂样氧化140 h后,TGO层由靠近陶瓷层的富(Cr,Al)2O3层、弥散其间的富Ni颗粒和靠近BC层的Al2O3层组成;TGO的生长速度先由Al与O2化学反应速度决定,接着受BC层金属元素扩散速度影响,最后由化学反应速度和扩散速度共同控制;减少TGO中的有害氧化物含量以降低涂层内的应力,可有效提高涂层的使用寿命。     

Microstructural changes to metal bond coatings on gas turbine alloys with time at high temperature

Complex coating systems are required to protect nickel-based super alloys from high temperature oxidation and corrosion. Industrial gas turbine blades and heat shields are generally plasma sprayed with a metal bond coating containing nickel, chromium, cobalt, aluminium and yttrium, and then an external thermal barrier coating of yttria-stabilised zirconia is applied. In this study, samples of an IN939 alloy heat shield with both a metal bond coat and a ceramic thermal barrier coating have been heated in air at high temperature for up to 2000 hours to assess the long term stability of the metal bond coat. Polished sections of the heat treated samples were examined by SEM and EDX to determine microstructural changes. The Ni-Cr-Co-Al-Y coating was found to be a very effective barrier against oxidation; the only apparent oxidation being the growth of an alumina layer between the bond coat and ceramic thermal barrier coating. With time, the growth of the Ni₃Al phase in the metallic bond coat was observed, with extensive diffusion of other elements to and from the bond coat.     

Effect of the thickness of plasma-sprayed coating on bond strength and thermal fatigue characteristics

NiCrAlY bond coat and ZrO2–8 wt% Y2O3 top coat with various thicknesses were deposited on Hastelloy X by plasma spraying. Residual stress was calculated by the finite element method (FEM) to explain the variations in the bond strength and thermal fatigue characteristics with the thickness of the bond coat and top coat. The bond strength of thermal barrier coatings (TBCs) increased with decreasing maximum residual stress in the y-direction of the top coat. The thermal fatigue characteristics increased with decrease of the maximum principal residual stress of the top coat and the thickness of oxidation layer of the bond coat.     

Degradation of thermal barrier coatings due to thermal cycling up to 1150°C

The degradation of thermal barrier coatings (TBCs) due to thermal cycling up to 1150°C has been studied. During thermal cycling, the bond coat in the TBCs was oxidised to form an alumina and a mixed oxide layer between the top coat of yttria stabilised zirconia (YSZ) and the bond coat of MCrAlY alloy. The mixed oxide layer mainly consists of -Cr₂O₃ and (Ni,Co)(Cr,Al)₂O₄ spinel phases, which are formed above the -alumina layer. Interestingly, the alumina layer gradually disappeared during the oxidation while the content of chromium in the mixed oxide increased with increasing oxidation time. As the oxidation accelerated after the disappearance of the alumina layer, cracks initiated and propagated in the mixed oxide layer near the YSZ. Eventually, the crack propagation induced the spallation of some YSZ top coatings after the 2000 h oxidation.     

Effect of platinum on the oxide-to-metal adhesion in thermal barrier coating systems

An investigation was conducted to determine the role of Pt in a thermal barrier coating system deposited on a nickel-base superalloy. Three coating systems were included in the study using a layer of yttria-stabilized zirconia as a model top coat, and simple aluminide, Pt-aluminide, and Pt bond coats. Thermal exposure tests at 1,150 °C with a 24-h cycling period to room temperature were used to compare the coating performance. Additional exposure tests at 1,000, 1,050, and 1,100 °C were conducted to study the kinetics of interdiffusion. Microstructural features were characterized by scanning electron microscopy and transmission electron microscopy combined with energy dispersive X-ray spectroscopy as well as X-ray diffraction. Wavelength dispersive spectroscopy was also used to qualitatively distinguish among various refractory transition metals. Particular emphasis was placed upon: (i) thermal stability of the bond coats, (ii) thickening rate of the thermally grown oxide, and (iii) failure mechanism of the coating. Experimental results indicated that Pt acts as a “cleanser” of the oxide-bond coat interface by decelerating the kinetics of interdiffusion between the bond coat and superalloy substrate. This was found to promote selective oxidation of Al resulting in a purer Al₂O₃ scale of a slower growth rate increasing its effectiveness as “glue” holding the ceramic top coat to the underlying metallic substrate. However, the exact effect of Pt was found to be a function of the state of its presence within the outermost coating layer. Among the bond coats included in the study, a surface layer of Pt-rich γ′-phase (L1₂ superlattice) was found to provide longer coating life in comparison with a mixture of PtAl₂ and β-phase.     

The effect of bond coat oxidation on the microstructure and endurance of a thermal barrier coating system

Abstract

Isothermal oxidation tests have been carried out on a thermal barrier coating (TBC) system consisting of a nickel-based superalloy, CoNiCrAlY bond coat applied by HVOF and yttria-stabilised zirconia (YSZ) top coat applied by EB-PVD. Bond coat microstructure, coating cracking and failure were characterised using high resolution scanning electron microscopy complemented with compositional analyses using energy dispersive X-ray spectrometry. A protective alumina layer formed during the deposition of the YSZ top coat and this grew with sub-parabolic kinetics during subsequent isothermal oxidation at temperatures in the range 950 to 1150°C. After short exposures at 1050°C and final cooling, small sub-critical cracks were found to exist within the YSZ but adjacent to bond coat protuberances. Their formation is related to the development of local tensile strains associated with the growth of an alumina layer (TGO) on the non-planar bond coat surface. However, for the specimens examined, these cracks did not propagate, in contrast to other TBC systems, and final spallation was always found to have occurred at the bond coat/TGO interface. This shows that the strain energy within the TGO layer made a significant contribution to the delamination process.